Quaternized perfluoroalkane sulfonamido nu-halomethyl carboxylic amides and a process for treating textiles therewith



United States Patent .0,

QUATERNIZED PERFLUQROALKANE SULFONA- MIDO N-HALQMETHYL CARBOXYLIC AMIDESAND A PROCESS FOR TREATWG TEXTILES THEREWITH Harvey A. Brown, EastOakdale Township, Washington County, and Robert J. Koshar, LincolnTownship, Washington County, Minn., assignors to Minnesota Mining andManufacturing Company, St. Paul, Minn, a corporation of Delaware NoDrawing. Filed May 2, 1960, Ser. No. 25,901 5 Claims. (Cl. 8116.2)

This invention relates to quaternized halomethylamides and moreparticularly to certain new quaternized perfluoroalkanesulfonamidoN-halomethyl carboxylic amides, and to a process for rendering textilessoil-resistant as well as oil and water repellent.

The novel quaternized halomethyl amides of the invention contain aquaternary ammonium group attached to a perfiuoroalkyl group through asulfonamido-alkylene carboxyarnide radical. The quaternary ammoniumgroup forms the cation of a salt of which the anion is a halide ion. Itwill be evident that the terms quaternary ammonium group and quaternizedN-halomethyl group have reference as to the hydrophilic portion of themolecule and are substantially synonymous. When the perfluoroalkyl groupcontains from about 4 to about 12 fully fiuorinated carbon atoms, it hasbeen found that the novel compounds of the invention can be employed astextile finishes, and particularly to treat fibrous materials such ascotton, Wool, nylon, silk, rayon, polyacrylate and polyacrylouitrilefibers and the like to produce a soil-resistant, waterand oil-repellentfinish for such materials without thereby altering either the color ortensile strength.

While it has heretofore been found possible to produce valuable anduseful soil-resistance, and oiland waterrepellency, in wool and certainsynthetic fibers, it has been diflicult to produce lasting effects onthe cellulosic fibers. The finishes heretofore developed for thispurpose, such as those which employ amide-quaternary amines as describedin United States Patent No. 2,303,191, have been relatively easilyremoved, often by a single laundering operation. They have also requiredthe deposit of relatively large amounts of the treating agent on thefibers, as compared with the compositions of the present invention.

It is an object of this invention to provide quaternary ammoniumcompounds possessing fluorocarbon tails.

Another object of this invention is to provide agents by means of whichfibrous materials can be rendered oiland water-repellent.

Another object of this invention is to provide agents by means of whichcellulosic materials and particularly cotton fibers can be renderedlastingly oiland waterrepellent.

A further object of this invention is to provide oiland water-repellentcellulosic materials such as cotton cloth.

Still another object of the invention is to provide a process forrendering cellulosic materials soil-resistant.

Other objects will become apparent hereinafter.

In accordance with the above and other objects of this invention certainnovel halomethylarnides have been discovered to be useful for theproduction of quaternary ammonium salts containing a perfluorocarbontail, and that the resulting quaternized compounds produce lasting3,147,066 Patented Sept. 1, 1964 ICC oiland water-repellency whenapplied to cellulosic fabrics and fibers and the like as well asnoncellulosic fibers and materials. These quarternary ammonium salts canbe represented by the formula:

wherein R, is a pertluoroalkyl group containing 4 to 12 carbon atoms, mis an integer from 2 to 12, R is an alkyl group containing 1 to 6 carbonatoms, Q is a radical of a tertiary nitrogenous base and X is chlorineor bromine.

It is important that the perfluorocarbon tail contain at least fourcarbon atoms, and the preferred number is six to ten. A terminalfluorocarbon chain of this minimum length is required in order toinsolubilize and render the end of the molecule both hydrophobicandoleophobic.

The perfiuorocarbon tail structure may include an oxygen atom linkingtogether two perfluorinated carbon atoms, or a nitrogen atom linkingtogether three perfiuorinated carbon atoms, since these linkages arevery stable and do not impair the inert and stable fluorocarboncharacteristic of the structure. The R, groups can accordingly be aperfluoroalkyl group (C F a perfluorocycloalkyl group (C F or asubstituted perfiuoroalkyl group (C F O or (C F N.

The perfluorocarbon tail of the molecule is inert, non-polar, and isboth hydrophobic and oleophobic. It is repellent not only to water butto oils and hydrocarbons, It imparts unique surface active and surfacetreating properties not possessed by corresponding compounds having ahydrocarbon tail, the latter being oleophilic and highly soluble in oilsand hydrocarbons.

It has been found that the quaternized N-(halomethyl) amides of theinvention can be applied to woven and nonwoven fabrics as more fullydescribed hereinafter to provide oiland Water-repellency with improvedresistance to laundering and dry cleaning.

The quaternized N-(halomethyl)amides of the invention may be used as thesole component in the treating vehicle or as a component in a complexmulti-ingredient formulation. For instance, excellent water and oilrepellency and soil resistance is obtained on textile fabrics which aretreated simultaneously with the quaternized N-(halomethyDamides andconventional finishes, such as mildew preventatives, moth resistingagents, crease resistant resins, lubricants, softeners, sizes, flameretardants, anti-static agents, dye fixatives, and water repellents. Inthe treatment of paper the quaternized N-(halomethyl) amide may bepresent as an ingredient in a wax, starch, casein, elastomer or wetstrength resin formulation.

In addition to oil and water repellency and soil resist? anceproperties, the quaternized N-(halomethyl)amides may be used to impartlower surface adhesion values and lower coefiicients of friction tosubstrates. Accordingly, they may also be used as mold release agents,for example, on wooden concrete-forms, and related applications.

In the treatment of fabrics and fibrous materials, the quaternizedN-(halomethyl)amides of the invention may be employed in conjunctionwith other treating agents, such as crease resisting resins, sizes,softeners, and water repellents, by concurrent or sequential treatments.Known treating agents of these classes are as follows. Crease resistingresins: Urea-formaldehyde resins, ethylene urea-formaldehyde resins,melamine-formaldehyde resins, triazine-formaldehyde resins, epoxyresins, and polyglycol acetals.

Sizes: Starch, casein, glue, polyvinyl alcohol, polyvinyl acetate,methyl cellulose, carboxymethyl cellulose. Softeners: Polyethyleneglycols, polyethylene, dimethyl polysiloxanes, amines and amides derivedfrom fatty acids and ethylene oxide condensation products of such aminesand amides.

Water repellents: Waxes, aluminum salts of fatty acids, silicone resins,chromium complexes of fatty acids, Nalkyl amidomethyl pyridinium salts,and melamineformaldehyde resin condensates with amides from fatty acids.

The compounds of the invention are prepared by the action offormaldehyde and hydrogen halide, e.g. hydrogen bromide or hydrogenchloride, on the amide to produce an N-(halomethyl)amide which is notusually isolated but is readily converted to a quaternary ammonium saltdirectly by addition of a tertiary nitrogenous base such as pyridine.The process is conveniently carried out out by passing the selectedanhydrous hydrogen halide in gaseous form into a solution of the amideand paraformaldehyde in an inert solvent, such as toluene, benzene andthe like, until there is substantially no further absorption of thehydrogen halide. As the reaction is not strongly exothermic, notemperature control is required, although heating from about 25 C. to100 C. (depending to an extent on the boiling point of the solvent used)may help to insure completion of the reaction. Although acids aresometimes employed for the cleavage of amides, this does not appear tooccur during the reaction even though the strongly acidic hydrogenhalides are employed.

The omega-perfluoroalkanesulfonamido-alkanoic acids from which theamides employed as starting materials in the process of the inventionare readily available by the procedure described in US. Patent No.2,809,990 and particularly described in Examples 4 and thereof. Thesodium derivative of an N-alkyl-perfluoro-alkanesulfonamide is reactedwith an alkyl omega-haloalkanoate to produce the corresponding alkylomega-perfluoroalkanesulfonamido alkanoate which is found can beammonolyzed directly to the amide with some difficulty or can besuccessively saponified, converted to the acid chloride and then to theamide. The omega-bromoalkanoic acids are converted to methyl or otheralkyl esters suitable for the above described reaction by conventionalmethods, such as heating a mixture of the acid and the selected alcoholin the presence of a catalytic amount of sulfuric acid. Illustrative ofsuitable omega-perfluoroalkanesulfonamidoalkanoic amides which can beproduced as described above from the known perfluoroalkanesulfonamidcsand omega-bromoalkanoic acids are:

3 (N-propyl-perfiuorobutanesulfonamido -propanoic amide 3(N-methyl-perfluorobutanesulfonamido) -propanoic amide 3(N-butyl-perfiuorooctanesulfonamido -propanoic amide 4-(N-butyl-perfluoro octanesulfonamido -butanoic amide 4-(N-hexyl-perfiuorododecanesulfonamido -butanoic amide 5-(N-methyl-perfiuorooctanesulfonamido) -pentanoic amide 5-(N-amyl-perfluorooctanesulfonamido) -pentanoic amide 6-(N-ethyl-perfiuorobutanesulfonamido -hexanoic amide 6- (N-butyl-perfluorododecanesulfonamido -l1exanoic amide 7-(N-methyl-perfiuorooctanesulfonamido) -heptanoic amide 9-(N-ethyl-perfiuorobutanesulfonamido -nonanoic amide 11-(N-methyl-perfiuorooctanesulfonamido) -hendecanoic amide I 13-(N-ethyl-perfluorobutanesulfonamido -tridecanoic amide Quaternization iseffected without isolation of the intermediate N-(halomethyl)-amide inthe inert solvent employed for the reaction after brief evaporation toremove excess hydrogen halide, or the reaction mixture may be furtherevaporated and some other solvent, such as anhydrous ether or dioxane,in which the quaternary salt is insoluble, may be added. The desiredtertiary organic base or amine is then added in the stoichiometricamount while maintaining the reaction in the range of about 25 C. toabout C. For this purpose any tertiary nitrogenous organic base which iscapable of forming a salt or a quaternary compound is suitable,including, for example, trialkyl amines such as trimethyl-amine,tributylamine and triododecylamine; cycloalkyl amines such astricyclohexylamine; aralkyl amines such as benzyl dimethylamine;arylamines such as dimethylaniline; and heterocyclic amines such aspyridine, picoline, lutidine, quinoline and the like can be used.Pyridine is particularly preferred for convenience and economy in theformation of cloth-treating agents as shown above.

Another procedure which is very convenient since it avoids the use ofhydrogen halide is to react the amide and paraformaldehyde directly withthe hydrohalide of the tertiary nitrogenous base, such as pyridinehydrochloride, in a suitable solvent such as the base, e.g., pyridine.Isolation is then carried out as described above adding, if desired, afurther amount of an organic solvent, such as an ether, for example,diethylether.

Examples of the quaternary ammonium salts of the perfluoro-alkylsubstituted amide compounds of the invention are:

3 (N-propyl) perfluorobutanesulfonamidopropionamidomethyl tributylammonium bromide 3 (N-methyl)perfluorobutanesulfonamidopropionamidomethyl pyridinium chloride 4(N-butyl-pertluorooctanesulfonamido) butanoamidomethyl picoliniumbromide 4 (N-hexyl-perfluorododecanesulfonamido) butanoamidomethylphenyl dimethyl ammonium chloride.

5 (N-methyl) pertluorooctanesulfonamidopentanoamidomethyl quinoliuiurnbromide 5 (N-amyl perfluorooctanesulfonamido) pentanoamidomethyltriethyl ammonium bromide 6 (N-ethyl)perfluorobutanesulfonamidohexanoamidomethyl trimethylammonium chloride 6(N-butyl) perfiuorododecanesulfonamidohexanoamidomethyltricyclohexylammonium chloride 7 (N-methyl)perfluorooctanesulfonamidoheptanoamidomethyl pyridinium chloride 9(N-ethyl-perfiuorobutanesulfonamido) nonanoamidomethyl pyridiniumbromide 11 (N-methy1-perfiuorooctanesulfonamido) hendecanamidomethylpyridinium chloride 13 (N-ethyl perfiuorobutanesulfonamido)tridecanamidomethyl trimethyl ammonium chloride.

The quaternized N-halomethylamides of the invention are employed fortreating woven or non-woven fibrous materials including wool, cotton,rayon, acetate, nylon and the like textiles, or paper, leather, wood,felt and similar organic fibrous constructions, and particularlycellulosic materials, by applying the selected quaternary ammoniumderivative, in aqueous medium buffered to about a pH in the range ofabout pH 5.5-6.5 and preferably about pH 6, to the cloth, removing anyexcess, drying at a temperature in the range of about 40 to 100 C. andheating the dried material to a temperature in the range of about 100 toC. for a period of the order of about 5 to 30 minutes to fix the finish.Thereafter the material is desirably treated with a mildly alkalinewashing to remove any residual acidic material formed upon decompositionof the quaternary compound during treatment, and dried. The treatmentmay be followed by a single aqueous wash before drying, if desired,although this may be omitted since subsequent laundering of the treatedfabric accomplishes the same purpose. The treatment may be termed afinishing treatment, since it is most usefully applied after weaving,forming, dyeing, weighting, filling or the like have been carried out.Cotton clothso treated appears to contain residual combined fluorine,indicating that at least a portion of the treating agent has reacted insome fashion, probably through the hydroxyl groups present in the fiber,although this hypothesis is not to be construed as limiting theinvention.

It is a surprising feature of cotton fabric treated with thesequaternary derivatives that not only is the cloth rendered oilandwater-repellent but also it possesses a considerable degree ofsoil-resistance, that is, it does not become soiled as readily asuntreated fabric. Furthermore, when soiled the fabrics thus treated arereadily launderable or dry-cleaned to return them to clean condition,after which they retain their oiland water-repellency, andsoil-resistance. The value of cloth so treated, for example, forchildrens clothes, or for uniforms for workers around oily machinery,automotive service men and the like will be readily apparent.

The color of the fabrics treated with the compositions of the invention,and their tensile strength, are not affected by the treatment. The handof cotton fabrics appears to be improved by the treatment.

It is noted that the finishing treatment of the invention can be appliedto resin-treated, wrinkle-resistant fabrics without adversely affectingthe desirable nonwrinkling feature of such fabrics.

The procedure for the preparation of the quaternized compounds of theinvention, and the application of the latter to fabrics, especiallycellulosic materials, are more specifically illustrated in the followingexamples, in which all parts are by weight and all percentages ofsolutions w/v. unless otherwise specified. It will be understood thatthese examples are illustrative only, to show the best mode presentlycontemplated of practicing the invention, and are not to be construed aslimiting as to the scope of the invention.

EXAMPLE 1 Omega-(N-methyl) perfluorooctanesulfonamidohendecanoic acid isprepared by the procedure described in Example 4 of U.S. Patent No.2,809,990. In that procedure, thestarting compound was N-methylperfluoroctanesulfonamide, C8F17SO2NHCH3, of which 51.3 grams wasneutralized with 2.3 grams of sodium dissolved in methanol. The solutionwas evaporated to dryness and 100 grams of acetone and 32.7 grams ofethylbromoundecylate, Br(CH COOC H were added. The mixture was refluxedfor 18 hours, poured into ether, and the sodium bromide precipitate wasfiltered off. The filtrate was vacuum distilled and 55.5 grams of a outwhich came over at 180-185 C. (0.75 mm.) was collected. This materialhad a melting point of 53 C. and was the ethyl ester of the desiredacid. A mixture of 40 grams thereof, 20 grams of acetic acid and 0.5gram of concentrated sulfuric acid was refluxed for 2 /2 hours,following which the ethyl acetate and acetic acid were distilled off.The residue was poured into ether and the solution was washed withwater. Evaporation of the ether yielded 35 grams of a white powder whichwas identified as the desired acid:

The acid thus prepared melts at 94 C.

A mixture of 135 parts of the above acid and 90 parts each of purifiedthionyl chloride and benzene is stirred together in a vessel equippedwith reflux condenser, first at room temperature (about 20 to 25 C.) andthen at 60 to 80 C. for 6 hours. The hydrogen chloride which is formedand entrained vopors are condensed in a trap cooled with solid carbondioxide. The reaction mixture is then evaporated first at about 10 mm.Hg at 90 C. and then at about C. at less than 1 mm. Hg to remove benzeneand unreacted thionyl chloride. On cooling, the light brown acidchloride corresponding to the starting acid, which remains as theresidue, solidifies. The acid chloride thus prepared melts at about 9899C.

Dry ammonia gas is passed into a stirred, externally cooled solution of123 parts of the above-prepared acid chloride is about 1400 parts of drydiethyl ether for about 2 /2 hours until reaction appears to have ceased(a drop in temperature is noted). A precipitate of the correspondingamide forms. The reaction mixture is filtered to recover the amide andthe crude product is rinsed with ether and dried. It is recrystallizedfrom hot 95 percent ethanol. The whitel1(N-methyl-perfluorooctanesulfonamido) hendecanamide thus prepared issoluble in chloroform, and insoluble in acetone or ether at roomtemperature.

Calculated for C2QH25F17N2SO3: C, N, 4.02%. Found: C, 34.7%; N, 3.93%.

in a vessel cooled to about 10 C. and provided with a mechaicalagitator, a condenser fitted with a drying tube and a thermometer areplaced 50 parts of the aboveprepared amide, 8.2 parts of pyridinehydrochloride (dried by distillation of benzene therefrom, 3 parts ofparafor-maldehyde and 245 parts of pyridine. The reaction mixture isheated. Some foaming occurs at 50 C. but the reaction mixture becomesclear at 65 C. Heating with agitation is continued for five hours at 75to C. and the mixture is then cooled to room temperature, whereupon aprecipitate of the desired pyridinium chloride salt is formed, and isrecovered by filtering. The solid crude product is slurried with about320 parts of acetone, collected and dried. The dried crude product isrecrystallized from acetone to provide omega-ll-(N-methylperfluorooctanesulfonamido) hendecanamidomethyl pyridiniumchloride, melting at about 144149, C. All the above filtrates arecombined and evaporated, and provide a further quantity of somewhat lesspure material. Thisquaternized halomethyl amideis soluble in chloroform,less so in acetone and insoluble in ether. A dilute solution in waterfoams when shaken.

Calculated for C H F N SO Cl-H O: C, 37.1%; N, 4.99%; H O, 2.14%. Found:C, 37.0%; N, 5.2%; H 0, 2.4%.

EXAMPLE 2 When the procedure of Example 1 above is applied to produceother N-alkyl perfluoroalkanesulfonamides by forming the sodium salt ofthe N-alkyl perfluorosulfonamide and condensing with an alkylomega-halo-alkanoate, other materials are obtained which can beconverted to quaternized N-halomethyl amides of the invention asdescribed in Example 1 or by the alternative and equivalent process ofhalomethylation and subsequent quaternization. Thus, when the sodiumsalt of'N-butyl-perfluorooctanesulfonamide is condensed withethyl-beta-bromopropionate, the ester ammonolyzed, the amidebromomethylated wtih paraformaldehyde and hydrogen bromide and thenquaternized with trimethylamine, there is obtained3-(N-butylperfluorooctanesulfonamido)-propionamidomethyl trimethylammonium bromide. Likewise, omega(N-ethyl-perfluorobutanesulfonamido)tridecanoamide-methyl phenyl diethylammonium chloride and omega (N-butyl perfluorododecanesulfonamido)hexanomidomethyl tricyclohexyl ammonium bromide are producedrespectively from the sodium salt of N-ethyl perfiuorobutanesulfonamideand ethyl omega-bromo-tridecanoate followed by ammonolysis,chloromethylation and quaternization with diethyl aniline and from thesodium salt of N-butyl-perfluorododecanesulfonamide and ethylomega-bromo-caproate followed by ammonolysis, bromomethylation andquaternization with tricylohexyl amrne.

7 EXAMPLE 3 The process for production of soil-resitsant, waterandoil-repellent cloth using the quaternary ammonium compounds of thisinvention is carried out as follows:

The treating solution is prepared by warming sodium acetate trihydrateand the selected quaternary ammonium treating agent in water at thedesired concentrations, which can range from about 0.1 to about 5percent, at about 30 to 40 C. until solution is effected. It is to benoted that at higher concentration the solution tends to becomemucilaginous, resembling a colloidal dispersion. The cloth to be treatedis soaked in the solution for 1 minute, removed and squeezed so that aweight of solution approximately equal to 75 to 125 percent of theweight of the cloth is retained. Under these conditions, the preferredconcentration of treating solution ranges from about 0.5 to about 2percent. The cloth is then dried for about 10 to 30 minutes at 40 to 100C. and the treatment is fixed by heating the cloth for about 5 to 30minutes at from about 100 to 140 C. The fixed, treated cloth is washedfor about 30 minutes in an aqueous solution containing 0.1 percent w./v.of sodium lauryl sulfate and 0.2 percent w./v. sodium carbonate, atabout 50 to 60 C., rinsed thoroughly and again dried. Other alkalineagents, such as dilute alkali metal hydroxides, bicarbonates, ammoniumhydroxide and the like can be used instead of alkali metal carbonates,to provide a mildly alkaline washing solution.

The effectiveness of the treatments is determined by means of tests forspray rating, oil repellency rating and visual estimation of soilrepellency both before further treatment and after one or more cycles oflaundering and/ or dry cleaning.

For test purposes, laundering is accomplished by washing in an automaticwashing machine of the stationary tub type using a detergent undernormal household procedures or by means of a standard 60-minute cycle ina Launder- O-Meter, using chip soap as specified in ASTM D-496.Dry-cleaning is performed by available commercial procedures employing,for example, perchloroethylene or naphtha.

Determination of water repellency rating is made by means of the SprayTest (Standard Test Method No. 22-52, published in the 1952 TechnicalManual and Yearbook of the American Association of Textile Chemists andColorists, vol. III, p. 136).

Oil repellency of the treated cloth is measured by a severe test inwhich its resistance to penetration by solutions of mineral oil inheptane is determined. (Higher proportions of heptane bring aboutquicker penetration.) A material wet by mineral oil alone in less than 3minutes rates zero, if it is only wet after 3 minutes it rates 50, whileresistance to penetration by a mixture of equal volumes of heptane andmineral oil rates 100. The ratings for resistance for 3 minutes are asfollows.

Percent heptane: Rating 50 20 .70 30 80 40 90 50 100 60 100+ A rating of70 or higher indicates a high degree of resistance to staining by saladoil and the like.

The 11 (N methyl) perfiuorooctanesulfonamidohendecanamidomethylpyridinium chloride of Example 1 is applied to kierboiled standardcotton jeans cloth in 2.5 percent w./v. solution containing 1 percent ofsodium acetate trihydrate as described hereinabove, drying at about 100C. for about 30 minutes, followed by curing at 150 C. for 5 minutes.

After a mildly alkaline wash as described above, rinsing and againdrying, it is subjected to tests before and after C) laundering (asdescribed) to determine oiland waterrepellency, with the followingresults:

Table I Spray Rating Oil Rcpcl- Percent F lency in Fabric Beforelaundering 00 100+ 0.71 After laundering 100+ 0. 09

A further sample using the same fabric is prepared using a 2.5 percentsolution of the treating agent and treating the cloth as set forthabove. It is dry-cleaned in two successive times and tested with thefollowing results:

Table II Spray Oil Rcpcl- Percent F Rating lcncy in Fabric Initially 0.58 After 1 dry cleaning 80+ 100+ 0. 40 After 2 dry cleanings 80- 100+ 0.23

0-as dark as control (untreated cloth sample) lslightly less dark thancontrol 2-more than about half as dark as control 3less than about halfas dark as control While the ratings are somewhat subjective, and mayvary to a certain extent as to the degree of soil involved, it issignificant that there is markedly less soiling of samples treated withthe compounds of the invention and this property is retained afterlaundering.

The synthetic soil mixture is prepared by blending the following:

Parts by weight Peat moss 38 Portlant cement 17.0 Kaolin clay 17.0Silica (800 mesh) 17.0 Furnace black (high leading, blue tone, powdered(Malacco)) 1.75 Red iron oxide 0.5 Mineral oil (heavy) 8.75

The blend is placed in a large pan and dried in a forced draftconvection oven for 2 hours at 50 C. and then ground in a ball mill. Thefinely divided material which is produced is stored in a desiccator overcalcium chloride or sulfuric acid.

The samples described above are rated at +3 when tested as above forsoil resistance before laundering or dry cleaning and the rating is onlyslightly decreased after these treatments.

Further samples are treated with omega-(N-methyl)-perfluorooctanesulfonamidohendecanamidomethyl pyridinium chloride asdescribed above using 1.4 percent of this treating agent and 1 percentsodium acetate trihydrate in water. Drying is carried out at 80 C. for30 minutes followed by curing for 5 minutes at C. The samples are thenWashed as above with a dilute aqueous alkaline solution of sodium laurylsulfate. Samples of a nylon upholstery fabric (designated A and B) andof an 80 x 80 count cotton fabric (designated C and D) are treated asabove and rated for oil and water repellency and soil resistance andthen cleaned repeatedly and again rated for oil and water repellency,with the following results:

Spray rating Dryeleaned once:

Oil rating 100 Spray rating Dry-cleaned thrice Spray rating The resultsshow that this quaternary ammonium compound is very efiective on cottonafter one dry-cleaning and still exerts some effect even after threedry-cleanings. It is more resistant to laundering. It will be apparentthat the treating solution containing afrorn about 1.4 to 2.5 percent ofthe treating agent is highly effective and that at least about 0.2percent fluorine should be present in the treated fabric after curing toprovide desirable oil, water and soil repellency after laundering.However, it is found that a solution containing 1.0 percent is also veryeffective and that as loW as 0.1 percent concentration can be used totreat fabrics, which then show excellent oil, Water and soil repellencybefore laundering. When the quaternized N-halomethyl amides of Example 2are employed to treat cotton fabrics under the conditions ofconcentration, time and temperature set forth above, substantially thesame results are obtained. Likewise treatment of wool, nylon and rayonfabrics by the above procedure confers oiland Water-repellency thereon.

The solutions used for treating fabrics as set forth above can also beapplied to paper with slight modifications in procedure to avoiddamaging the structure of the paper, which, as is well known, isweakened by treatment with Water. Thus, the excess of treating solutionis removed by permitting the paper to drip dry or by running the Webbetween rolls, while drying and fixing are accomplished by heating theindividual sheets or by hot-roll calendering long strips or continuousrolls. The treated paper is oiland water-repellent. The surface of woodis rendered repellent to oil and water and resistant to soiling bytreatment with the above solutions painted on, heated and subsequentlyneutralized and dried.

EXAMPLE 4 This example illustrates the use of the compositions of thisinvention in conjunction with chemically compatible treating agentswhich can be employed either to produce a multiplicity of results or asynergistic combination of results. Such effects may be sought whereincreased resistance to water is sought, even at slight expense of theoil repellency, or where both will be somewhat sacrificed to impartadditionally, for example, crease, crush or wrinkle resistance.

Thus, when untreated samples of 80 X 80 count cotton cloth are treatedas above with a 1 percent aqueous solution of the pyridinium chloride ofExample 1 containing additionally about perecnt of amelamine-formaldehyde condensate of the type used for imparting Wrinkleresistance, about 1 percent of an accelerator to advance the cure of theresin and 1 percent of sodium acetate trihydrate, dried for 10 minutesat 80 C. and cured for 5 minutes at 150 C., then rinsed with a solutionof an ammonium soap and cured for a further 6 minutes at 150 C., thesamples shown no noticeable discoloration and show both oilandwater-repellency as Well as soilresistance. The repellency is slightlyreduced by 3 laun- 10 derings but soil-resistance is retained. Thecrease-resistance conferred by the other additives is still evident.

Substantially the same results are obtained when the crease resistancepromoting treatment is applied first and the dried cloth is subsequentlytreated with a 1 percent aqueous solution of the pyridinium chloride ofExample 1 containing about 1 percent of sodium acetate trihydrate andcured and Washed as described above. It is thus apparent that thequaternized N-(halomethyl)amides of the invention can be usedconcurrently or sequentially with other treatments available in the art.

When samples of cotton jeans cloth are treated in duplicate with theagent of Example 1 above with and Without the addition of anN-alkylstearoamidomethyl pyridinium chloride representative ofcommercially accepted agents for imparting temporary water-repellency tocotton, it is found that there is slight reduction in oil-repellency andincrease in water-repellency in the sample treated with the combinationof agents.

What is claimed is:

1. A compound of the formula:

0 RtsO2l l(CH iNHOHzQ+X-' wherein R is perfluoroalkyl having 4 to 12carbon atoms, In is an integer from 2 to 12, R is a member of the groupconsisting of hydrogen and alkyl having from 1 to 6 carbon atoms, Q is atertiary nitrogenous organic residue selected from the group consistingof trialkylamino having 3 to about 36 carbon atoms, tricycloalkylaminohaving about 18 carbon atoms, aralkylamino having about 8 carbon atoms,arylamino having about 8 carbon atoms, pyridino, picolino, lutidino andquinolino, and X is a halogen of the group consisting of chlorine andbromine.

2. Omega (N methyl) 11 perfiuorooctanesulfonamidohendecanamidomethylpyridinium chloride.

3. The process for rendering fibrous materials Waterand oil-repellent,which comprises treating thefibrous material with a compound of theformula:

wherein R is perfiuoroalkyl having 4 to 12 carbon atoms, In is aninteger from 2 to 12, R is a member of the group consisting of hydrogenand alkyl having from 1 to 6 carbon atoms, Q is a tertiary nitrogenousorganic residue selected from the group consisting of trialkylaminohaving 3 to about 36 carbon atoms, tricycloalkylamino having about 18carbon atoms, aralkylamino having about 8 carbon atoms, arylamino havingabout 8 carbon atoms, pyridino, picolino, lutidino and quinolino, and Xis a halogen of the group consisting of chlorine and bromine; in aqueousmedium bufitered to about pH 5.5 to 6.5, drying the treated fibrousmaterial and heating the dried, treated material to a temperature in therange of about C. to C. for about 5 to 30 minutes.

4. A fabric finished with a compound of the formula:

wherein R is perfluoroalkyl having 4 to 12 carbon atoms, In is aninteger from 2 to 12, R is a member of the group consisting of hydrogenand alkyl having from 1 to 6 carbon atoms, Q is a tertiary nitrogenousorganic residue selected from the group consisting of trialkylaminohaving 3 to about 36 carbon atoms, tricycloalkylamino having about 18carbon atoms, aralkylamino having about 8 carbon atoms, arylamino havingabout 8 carbon atoms, pyridino, picolino, lutidino and quinolino, and Xis a halogen of the group consisting of chlorine and bromine; wherebythe fabric contains residual combined fluorine and has oilandwater-repellent properties.

5. A cellulosic fabric having oiland Water-repellent properties togetherwith soil resistance and good hand,

1 1 finished with omega-(N-methyD-ll perfluorooctanesul- 2,233,296fonamidohendecanamidomethyl pyridinium chloride. 2,292,997 2,412,054References Cited in the file of this patent 2,809,990

UNITED STATES PATENTS 5 2,146,392 Baldwin et a1 Feb. 7, 1939 2,216,406Austin Oct. 1, 1940 12 Nelles Feb. 25, 1941 Hentrich Aug. 11, 1942McClellan Dec. 3, 1946 Brown et a1 Oct 15, 1957 OTHER REFERENCES Noller:Chemistry of Organic Compounds, 2nd edition, page 241 (Saunders) (1957).

1. A COMPOUND OF THE FORMULA:
 5. A CELLULOSIC FABRIC HAVINGN OIL- ANDWATER-REPELLENT PROPERTIES TOGETHER WITTH SOIL RESISTANCE AND GOOD HAND,FINISHED WITTHOMEGA-(N-METHYL)-11-PERFLUOROOCTANESULFONAMIDOHENDECANAMIDOMETHYLPYRIDINIUMCHLORIDE.